1,3-bis(n,n-diloweralkyl-thiocarbamoylthic(2-tertiary aminopropane) compounds)

ABSTRACT

Compounds of the formula WHEREIN A represents a tertiary amino group and R represents a N,N-diloweralkylthiocarbamoyl group are useful as pesticides.

United States Patent Sakai et al.

[54] l,3-BIS(N,N-DILOWERALKYL- THIOCARBAMOYLTHICQ-TERTIARY AMINOPROPANE)COMPOUNDS) [72] Inventors: Mlchlhlko Sakai, Kyoto; Mnsayuki Kilo,

Osaka, both of Japan; I'Iikoichi Hlgiwara, deceased, late of Osaka,Japan by Reiko Hagiwara, executor; Kazuo Konkhi, Osaka, Japan [73]Assignee: 'Iakeda Chemical Industries, Ltd., Osaka,

Japan [22] Filed: Feb. 13,1970

[21] Appl.No.: 11,346

Related US. Application Data [62] Division of Ser. No. 612,059, Sept.22, 1966, Pat. No. 3,501,502, Division of Ser. No. 205,088, June 25,1962, Pat. No. 3,318,936.

[ 52] [1.8. CI. ..260/455 A [51] Int. Cl ...C07c 155/08 [58] Field ofSearch ..260/455 A [56] References Cited UNITED STATES PATENTS 2,411,21911/1946 Mathes ..260/455 [151 3,666,786 [451 May 30, 1972 Hagiwara eta1., Aminopropane 1,3- dihaiides 1963) CA 59 p. 11250 1963) PrimaryExaminer-Elbert L. Roberto Assistant Examiner-G. HollrahAttorney-Wenderoth, Lind & Ponack [57] ABSTRACT Compounds of the formulaA R-S-CHrH-CHr-S-R wherein A represents a tertiary amino group and Rrepresents a N,N-diloweralkylthiocarbamoyl group are useful aspesticides.

2 Claims, No Drawings l ,3-BIS(N ,N-DILOWERALKYL'I'KHOCARBAMOYL'IHICQ-TERTIARY AMINOPROPANE) COMPOUNDS) This applicationis a divisional application of Application Ser. No. 612,059, filed Sept.22, l966, now US. Pat. No. 3,501,502, which application is in turn adivisional application of Application Ser. No. 205,088, filed June 25,1962, now US. Pat. No. 3,318,936.

This invention relates to novel compounds and specified use thereof.More particularly, the instant invention is concerned with the new anduseful compounds having in their molecule a tertiary amino group and twosubstituted thio groups, and with the utilization thereof as pesticidesfor e.g. agricultural and sanitary purposes.

The objective compounds provided by the present invention arerepresented by any of the formulas (la), ([11) and (lc);

wherein n is an integer from to 4, A stands for a tertiary amino group,and R stands for two hydrogen atoms, two univalent S-substituting groupsor a bivalent S-substituting group.

To simplify the disclosure, the terms S-substituting group" andsubstituted thio group" will be frequently used in this specificationfor expressing the atomic group combining or to be combined to thesulphur atom or atoms illustrated in the formulas (l) and the thio groupsubstituted with the said S- substituting group i.e. S(. R)respectively.

More concretely stated, S-substituting group" is, for example, cyano,amidino, an N monosubstituted amidino group, a lower hydrocarbonresidue, a lower carboxylic acid acyl group, a lower sulfonic acid acylgroup, a lower sulfinic acid acyl group, anN,N-diloweralkyl-thiocarbamoyl group, an N,N'diloweralkylcarbamoylgroup, an 0,0-diloweralkylphosphono group, an0,0-diloweralkyl-thiophosphono group, a loweralkoxy-carbonyl group, aloweralkoxy-thiocarbony] group, thiocyanato or a mercapto groupsubstituted with a lower hydrocarbon residue as the univalent groups,or,

for example, carbonyl, thiocarbonyl, a methylene group substituted witha lower hydrocarbon residue or the bivalent group represented by thepart except R of the formula selected from the formulas (I) as thebivalent group.

It was further found by the present inventors that these novel compoundsillustrated by the formulas (I) have a remarkable activity for killinginsects, mites and nematodes, and therefore are useful for new-typepesticides.

The principal object of the instant invention is, therefore, to providea series of novel compounds represented by the formulas (I) and theirsalts, which are useful for killing harmful animals such as insects,mites and nematodes.

Further object is to provide pesticidal compositions which can desirablybe applied for agricultural and sanitary purposes to combat harmfulinsects including mites and nematodes, the compositions beingcharacterized by containing one or more kinds of the compoundsrepresented by the formulas (l) including those in the form of acidsalts.

These objective compounds can generally be prepared through any of thefollowing courses.

A. The substituted thio groups are introduced into the correspondingdihalogeno compounds. For this process, dihalogeno compounds representedby one of the formulas (Ila), (H12) and (lie):

(CH2) r-A, OH2-OH-CHz-(CH) -A wherein n and A have the same meanings asin the formulas (I), and each of X and X represents a halogen atom, e.g.chlorine, bromine and iodine, can be used and one of the startingcompounds represented by the formulas (II) is allowed to react with areactant to replace the halogen atom attached to the hydrocarbonskeleton with a mercapto group or with the substituted thio group. Assuch a reactant, for example, hydrogen sulfide or its salt (such assodium sulfide, potassium sulfide, ammonium sulfide or a chemicalequivalent thereof) to replace the halogen atoms with mercapto groups,thiocyanic 'acid or its salt (such as sodium thiocyanate, potassiumthiocyanate, ammonium thiocyanate or a chemical equivalent thereof) toreplace the halogen atoms with thiocyanato groups (SCN); a mercaptan(such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butylmercaptan, hexyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, thiophenol or chemical equivalent thereof) or a mercaptide thereof (such asthe sodium mercaptide, the potassium mercaptide, the zinc mercaptide,the silver mercaptide or a chemical equivalent thereof of the mercaptansas exemplified above) to replace the halogen atoms with two mercaptogroups both substituted with a lower hydrocarbon residue; thiourea or anN-substituted thiourea (such as methyl thiourea, ethyl thiourea, propylthiourea, allyl thiourea, butyl thiourea, benzyl thiourea, phenylthiourea or a chemical equivalent thereof) or an acid salt thereof (suchas the hydrochloride, the hydrobromide or a chemical equivalent thereofof thiourea or of the N- monosubstituted thiourea as exemplified above)to replace the halogen atoms with amidinothio groups; a lowerthiocarboxylic acid (such as thiolacetic acid, thiolbenzoic acid,thiolfuroic acid or a chemical equivalent thereof) or a salt thereof(such as the sodium salt, the potassium salt, the ammonium salt, thelead salt or a chemical equivalent thereof the thiolcarboxylic acids asexemplified above) to replace the halogen atoms with lower carboxylicacyl-thio groups; a lower thiolsulfonic acid (such as methanethiolsulfonic acid, ethane thiolsulfonic acid, propane thiolsulfonicacid, benzene thiolsulfonic acid, p-toluene thiolsulfonic acid or achemical equivalent thereof) or a salt thereof (such as the sodium salt,the potassium salt, the ammonium salt or a chemical equivalent thereofof the thiolsulfonic acids as exemplified above) to replace the halogenatoms with lower sulfonic acid acyl-thio groups; a lower thiolsulfinicacid (such as methane thiolsulfinic acid, ethane thiol-sulfinic acid,propane thiolsulfinic acid, benzene thiol-sulfinic acid, p-toluenethiolsulfinic acid or a chemical equivalent thereof of the thiolsulfinicacids as exemplified above) to replace the halogen atoms with lowersulfinic acid acyl-thio groups; an N,N-disubstituted dithiocarbamicacid, such as N,N-diethyldithiocarbamic acid, N,N-dipropyldithiocarbamicacid, N,N-dibutyldithiocarbamic acid, N,N- dipentyldithiocarbamic acidor a chemical equivalent thereof) or a salt thereof (such as the sodiumsalt, the potassium salt, the ammonium salt or a chemical equivalentthereof of the N,N-disubstituted dithiocarbamic acids as exemplifiedabove) to replace the halogen atoms with theN,N-diloweralkylthiocarbamoylthio groups; an N,N-disubstitutedthiolcarbamic acid (such as N,N-dimethylthiolcarbamic acid, N,N-dipropylthiolcarbamic acid, N,N-dibutylthiolcarbamic acid,N,N-dipentyltl'iiolcarbamic acid or a chemical equivalent thereof) or asalt thereof (such as the sodium salt, the potassium salt, the ammoniumsalt or a chemical equivalent thereof of the N,N-disubstitutedthiolcarbamic acids as exemplified above) to replace the halogen atomswith the N,N-diloweralkyl-carbarnoylthio groups; an 0,0'-disubstitutedthiolphosphoric acid (such as 0,0-dimethyl hydrogen thiolphosphate,0,0'-diethyl hydrogen thiolphosphate, methyl-O'-ethyl hydrogenthiolphosphate, 0,0'-dipropyl hydrogen thiolphosphate, 0,0'-dibutylhydrogen thiolphosphate, 0,0-dipentyl, hydrogen thiolphosphate or achemical equivalent thereof) or a salt thereof (such as the sodium salt,the potassium salt, the ammonium salt or a chemical equivalent thereofof the 0,0'-disubstituted thiolphosphoric acid as exemplified above) toreplace the halogen atoms with the 0,0-diloweralkylphosphonothio groups;an 0,0-disubstituted thiolthionphosphoric acid (such as 0,0'-dimethylhydrogen thiolthionphosphate, 0,0-diethyl hydrogen thiolthionphosphate,O-methyl-O'-ethyl hydrogen thiolthionphosphate, 0,0-dipropyl hydrogen 1thiolthionphosphate, 0,0'-dibutyl hydrogen thiolthionphosphate,0,0'-dipentyl hydrogen thiolthionphosphate or a chemical equivalentthereof) or a salt thereof (such as the sodium salt, the potassium saltor a chemical equivalent thereof of the 0,0'-disubstitutedthiolthionphosphoric acid as exemplified above) to replace the halogenatoms with the 0,0'-dilowera.lkylthiophosphonothio groups; a xanthogenicacid (such as methyl xanthogenic acid, ethyl xanthogenic acid, propylxanthogenic acid, pentyl xanthogenic acid or a chemical equivalentthereof) or a salt thereof (such as the sodium salt, the potassium salt,the ammonium salt or a chemical equivalent thereof of the xanthogenicacid as exemplified above) to replace the halogen atoms with theloweralkoxythiocarbonylthio groups; a salt (such as the sodium salt, thepotassium salt or the ammonium salt) of an O-monoloweralkylester (suchas the methyl, the ethyl or the propyl ester) of monothiolcarbonic acidto replace the halogen atoms with the loweralkoxycarbonylthio groups; asalt of thiosulfuric acid (such as sodium thiosulfate, potassiumthiosulfate or ammonium thiosulfate) to replace the halogen atoms withsulfothio groups in the form of partial salts i.e. in the form of Buntessalts; an alkali metal trithiocarbonate to replace the halogen atomswith a group S-CS-S; and hydrogen disulfide or its salt (such as sodiumdisulfide, potassium disulfide or ammonium disulfide) to replace thehalogen atoms with dithio groups between two molecules of the startinghalogeno compounds whereby the l,2,6,7-tetrathiecane ring or thel,2,5,6- tetrathiocane ring is formed can be used.

The reaction is carried out by allowing the dihalogeno compound of anyof the formulas (II) to react with the thio] compound or its functionalderivative as mentioned above. Usually there is used the thio] compoundor its functional derivative in an amount of not less than twice as muchas the used dihalogeno compound on molar basis. When the thiol compoundor its functional equivalent in about equimolar amount relative to thedihalogeno compound is used, the corresponding monosubstituted thiomonohalogeno compound is produced as a principal product, on which asimilar reaction for replacing the residual halogen atom with the sameor the other substituted thio group or a mercapto group is repeatedlybrought about; this means is conveniently applied for producing thoseobjective products whose two substituted thio groups are different fromeach other.

The reaction is preferably carried out in an appropriate solvent such aswater, methanol, ethanol, propanol, acetone, methyl ethyl ketone,cyclohexanone, ether, dioxane, tetrahydrofuran, dimethylformamide,pyridine, 2-methyl-5- ethylpyn'dine, benzene, chloroform or a mixture oftwo or more kinds of these, the solvent should be selected in accordancewith the kind of the used thiol compounds. Usually, the reaction cansmoothly proceed at room temperature and, if desired or if required, thereaction mixture may, of course, be heated or cooled according to theprogress of the reaction.

B. The tertiary amino group represented by A in the aforepresentedformulas (l) is introduced into the corresponding halogeno compoundsrepresented by one of the formulas (Illa), (lllb) and (lIIc):

wherein n and R have the same meaning as in the formulas (l), and Xrepresents a halogen atom, e.g. chlorine, bromine and iodine. Thestarting halogeno compound represented by one of the formulas (III) isallowed to react with a secondary amine, or with a primary amine, and,in the latter case, followed by a further procedure of substitution ofhydrogen atom in the resulting secondary amine with a halogenatedhydrocarbon or with a ketone or an aldehyde and formic acid according tothe so-called Leuckart Reduction (or Reaction)" However, the reactionwith a secondary amine is more advantageous than the reaction with aprimary amine, since not only is there no need to carry out thesubsequent reaction in the case of the former reaction, but also thereis less opportunity to produce a mixture of secondary amine and tertiaryamine that in the case of the latter reaction. As the secondary amine tobe used for the former reaction, for example, dimethylamine,diethylamine, methyl ethyl amine, dipropylamine, dibutylamine,diamylamine, di-sec-butylamine, di-iso-butylamine, dicyclohexylamine,diphenylamine, monomethylaniline, monoethylaniline, monomethyltoluidine,pyrro], pyrroline, pyrrolidine, piperidine, piperazine, morpholine,thiomorpholine, azirane (ethylenimine) or a chemical equivalent thereofcan be used.

The reaction is carried out by allowing the halogeno compound of theformulas (ill) to react with the aforementioned amine in an excess ofthe amine or in an appropriate organic solvent such as methanol,ethanol, propanol, acetone, dioxane, dimethylformamide, tetrahydrofuran,benzene, toluene or a chemical equivalent thereof. As one mole ofhydrogen halide is produced as the reaction proceeds, one further moleof the used amine may be consumed for neutralizing the produced hydrogenhalide, if any other suitable alkali co-exists in the reaction mixture.Therefore, if it is desired to avoid the consumption of the used aminefor the neutralization, e.g. from the point of economical view, theprocedure may be somewhat modified in such a manner that a strong alkaliis gradually added to the reaction mixture containing the startinghalogeno compound and about equivalent of the amine. In general thereaction can be promoted by heating at a temperature lower than 200 C.Of course, according to the kind of the used starting materials, thereare cases in which the reaction can be carried out smoothly at roomtemperature. Moreover, the reaction may be carried out under atmosphericpressure or under superatmospheric pressure if desired, but usually itis sufficient with pressure lower than 30 atmospheres.

When the substituted thio group is a thiol group substituted with alower hydrocarbon residue, another modified procedure can be applied forthe production of the objective compound. In this procedure, however, anoxo compound is used as the starting compound instead of the halogenocompound, and the reaction is carried out under reducing conditions. Thereducing conditions can be provided by allowing a reducing agent toexist in the reaction mixture or by subjecting the reaction mixture tocatalytic reduction. As the reducing agent, for example, an alkali metaland a lower alcohol, iron and hydrochloric acid, iron and acetic acid,sodium amalgam, or a chemical equivalent thereof can be used.

C. A product, which was produced by either procedure mentioned in item(A) or (B), can be changed into other compounds, also represented by theformulas (I), by modifying the substituted thio groups into some othersubstituted thio groups. The means for the modification are exemplifiedas follows:

a. Among the compounds of the formulas (I), those having two thiolgroups as the substituted thio groups are changed into those having twoS-S-R groups, wherein R represenm a lower hydrocarbon residue. One ofthe dithiol compounds is allowed to react with an agent for introducingS-R group, into the thiol groups. As the agent for introducing S-Rgroup, a variety of thiol esters can be used. For example, a thiol ester(such as methyl, ethyl, phenyl, benzyl or tolyl ester) of thiosulfuricacid or its water soluble salt (Buntes salts), a thiol ester of athiolsulfonic acid (such as a methanethiolsulfonate, anethanethiolsulfonate, a benzenethiolsulfonate, a toluenethiolsulfonateor a chemical equivalent thereof), a thiol ester of a thiolsulfinic acid(such as methanethiolsulfinate, an ethanethiolsulfinate,toluenethiolsulfinate or a chemical equivalent thereof), an ester ofthiothiocyanate, a sulfenyl halide (such as a sulfenyl chloride, asulfenyl bromide or a sulfenyl iodide) or any of their chemicalequivalents may be used. The hydrocarbon residue of theabove-exemplified thiol esters, the residue being to be introduced intothe objective compounds together with the sulphur atom to which theresidue is combined, may respectively be methyl, ethyl, propyl,isopropyl, ally], butyl, isobutyl, amyl, hexyl, heptyl, phenyl, tolyl,cyclohexyl, benzyl or their chemically equivalent group, for example.

The reaction is generally carried out in a suitable solvent such aswater, methanol, ethanol, dioxane, tetrahydrofuran, dimethylformamide,benzene, toluene, or a mixture of two or more kinds of them, andsmoothly proceeds in the medium adjusted to about pH 7.0 to 9.0 at roomtemperature. But, in some cases, favorable result may be obtained byheating the reaction mixture at a temperature lower than about 100 C.

b. The compounds of the formulas (I), which have two thiol groups as thesubstituted thio groups, are also changed into those having any ofcarboxylic acyl groups, sulfonic acyl groups, sulfinic acyl groups, acarbonyl group or a thiocarbonyl group as S-substituting groups. One ofthe dimercapto compounds or mercaptides thereof is allowed to react withan acylating agent.

As the carboxylic acylating agent, for example, a carboxylic acid (suchas formic acid, acetic acid, propionic acid, acrylic acid, butyric acid,isobutyric acid, crotonic acid, valeric acid, isovaleric acid, caproicacid, enanthic acid, sorbic acid, succinic acid, maleic acid, glutaricacid, acetoacetic acid, levulinic acid, chloroacetic acid,trichloroacetic acid, cyanoacetic acid, cyclopentanecarboxylic acid,hexahydrobenzoic acid, benzoic acid, chlorobenzoic acid, nitrobenzoicacid, furoic acid or a chemical equivalent thereof); its acid halide(such as an acid chloride, an acid bromide or an acid iodide of thecarboxylic acid as exemplified above), its acid anhydride (including ahomogeneous acid anhydride between two molecules of the same carboxylicacid as exemplified above; a mixed (heterogeneous) acid anhydridebetween the carboxylic acid as exemplified above and the othercarboxylic acid as exemplified above; a mixed acid anhydride between thecarboxylic acid as exemplified above and a volatile acid such ascarbonic acid mono ester, or an intramolecular acid anhydride when acarbon chain consisting of two or more carbon atoms is interposedbetween two carboxylic groups), the thiolcarboxylic acid correspondingto the carboxylic acid as exemplified above; the ketene corresponding tothe carboxylic acid as exemplified above when the carboxylic acid hasthe partial structure CI-I -CI-I -COOH; a lower alkyl ester of thecarboxylic acid or of thiolcarboxylic acid as exemplified above (such asthe methyl, the ethyl, or the propyl ester of the carboxylic acid or ofthe thiol carboxylic acid) or a chemical equivalent thereof may be used.

As the sulfonic acylating agent, for example, a sulfonic acid (such asmethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid,hexanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid,p-toluenesulfonic acid, cyclohexanesulfonic acid, phenylmethanesulfonicacid or a chemical equivalent thereof); its acid halide (such as an acidchloride, an acid bromide or an acid iodide of the sulfonic acid asexemplified above) or its acid amide can be used.

As the sulfinic acylating agent, for example, any of the sulfinic acidsor their acid halides corresponding to the sulfonic acids or their acidhalides as mentioned in the preceding paragraph can be used.

For introducing carbonyl or thiocarbonyl group as S-substituting groups,a carbonyl or thiocarbonyl halide (such as phosgene, carbonyl bromide,thiophosgene or thiocarbonylbromide) can be used.

The reaction is generally carried out in a suitable solvent such aswater, methanol, ethanol, propanol, dioxane, tetrahydrofuran, pyridine,dimethylformamide, a chemical equivalent thereof or a mixture of two ormore kinds of them, and usually proceeds in an alkaline to neutralmedium. Usually, the reaction can be carried out at room temperature,but is may be operated under cooling or heating when required.

In a similar way, the compounds of the formulas (I), which havemethylene or a methylene group substituted with a lower hydrocarbonresidue as the S-substituting groups, are produced by subjecting thedimercapto compounds or their mercaptides to a condensation reactionwith an aldehyde (such as formaldehyde, acetaldehyde, propionaldehyde,butyraldehyde, isobutyraldehyde, caproaldehyde, benzaldehyde,p-tolualdehyde or o-tolualdehyde) or an alkylidene halide (such asmethylene chloride, methylene bromide, ethylidene chloride, propylidenebromide, benzal chloride or a chemical equivalent thereof). By thereaction, a l,3-dithiolane ring or 1 ,3-dithiane ring is formed.

c. The compounds of the formulas (I), which have two lower hydrocarbonresidues or a methylene substituted with a lower hydrocarbon residue asS-substituting groups, are changed into those having two thiol groups asthe substituted thio groups, i.e. having hydrogen atoms in place of theS-substituting groups.

The reaction is carried out under reducing conditions and/or in thepresence of a heavy metal salt. In order to eliminate the hydrocarbonresidue attached to the sulphur atom, fairly strong reduction isrequired and there is used a rather strong reducing agent such as analkali metal (e.g. metallic sodium, metallic potassium, metalliclithium), the alkali metal as exemplified above and a lower alcohol(e.g. methanol, ethanol or a chemical equivalent thereof), the alkalimetal as exemplified above and an acid (e.g. acetic acid or a chemicalequivalent thereof), an amalgam of the alkali metal as exemplifiedabove, an alkali metal amide (e.g. sodium amide, lithium amide orpotassium amide), formic acid, or hydrogen in the presence of a metalliccatalyst (e.g. Raney nickel, platinum, palladium or a chemicalequivalent thereof). The reaction is usually carried out in a suitablesolvent such as methanol, ethanol, liquid ammonia, dimethylamine,diethylamine, pyridine, 5-ethyl-2-methylpyridine, dimethylformamide,diethylether, tetrahydrofuran, dioxane or a chemical equivalent thereof,selected suitably in accordance with the kind of the reducing agent tobe used.

In place of or together with the reducing agent, a heavy metal salt canbe used for the reaction to eliminate the hydrocarbon residue of thesubstituted thio group to form the dithiol compounds, which are producedin the form of the mercaptide of the used heavy metal and the subsequentintroduction of hydrogen sulfide into the suspension of the mercaptideaffords the free thiol compounds. As the heavy metal salt for thispurpose, for example, water-soluble salt of a metal such as lead,mercury or zinc can be used and the reaction is carried out in asuitable solvent such as water, chloroform, benzene, ether, theirchemical equivalent or two or more kind of them. In this case, heatingaccelerates desirably the reaction velocity.

By the reaction or reactions mentioned above, there can be produced thedesired compounds (I) such as:

l ,2-dimercapto-3-dimethylaminopropane,

l ,2-dithiocyanato-3-dimethylaminopropane,

1 ,2-bis( amidinothio)-3-dimethylaminopropane,

l,2-bis( benzylthio )-3-dimethylaminipropane,

I ,2-bis(benzyldithio)-3-dimethylaminopropane,

l ,2-bis( n-propyldithio )-3-dimethylaminopropane,

1 ,2-bis( benzoylthio )-3-dimethylaminopropane,

1 ,2-bis( furoylthio )-3-dimethylaminopropane,

1 ,2-bis( acetylthio )-3-dimethyla.minopropane,

l ,2-bis( n-hexylthio )-3-dimethylaminopropane,

l ,2-bis( methanesulfo nylthio )-3-dimethylaminopropane,

l ,2-bis( n-pr'opoxycarbonylthio )-3-dimethylaminopropane,

l ,2-bis( di-n-propoxyphosphinothio)-3- dimethylaminopropane,

1 ,2-bis( n-hexyldithio)-3-dimethylaminopropane,

1 ,2-bis( 4-ethoxycarbonylbutyrylthio )-3- dimethylaminopropane,

l ,2-bis( methyldithio )-3-( 3-dimethylaminopropyl )propane,

l ,2-bis( p-toluenesulfonylthio )-3-diethylaminopropane,

1 ,2-bis( phenoxycarbonylthio )-3-diethylaminopropane,

l ,2-bis( benzylsulfinylthio 3-diethylaminopropane,

l ,2-bis( methylethylcarbamoylthio )-3- diethylaminopropane,

l,2-bis( 3-ethoxycarbonylpropionylthio )-3- diethylaminopropane,

l ,2-bis(ethoxy-thiocarbonylthio )-3-diethylaminopropane,

I ,2-bis(n-propyldithio)-3-diethylaminopropane,

l,2-bis( amidinothio )-3-methylethylaminopropane dihydrochloride,

l ,2-bis( benzylthio )-3-methylethylaminopropane,

1 ,2-bis( diethylcarbamoylthiol )-3-diallylaminopropane,

l ,2-bis( benzoylthio )-3-di-n-amylaminopropane,

l ,2bis( benzylthio )-3-dibenzylaminopropane,

l ,2-bis( benzensfulfinylthio)-3-dibenzylaminopropane,

l ,2-bis( n-propyldithio)-3-dibenzylaminopropane,

l,2-bis( phenylthiol )-3-phenylethylaminopropane,

l ,2-bis( n-amylthiol )-3-cyclohexyl-n-propylaminopropane,

l ,2-bis( dibenzylcarbamoylthio )-3-dicyclohexylaminopropane,

l,Z-dimercapto-3-dicyclohexylaminopropane,

l ,2-bis( benzylthio )-3-piperidinopropane,

1 ,2-bis( benzenesulfinylthio )-3-piperidinopropane,

l ,2-bis( di-n-propoxyphosphinothio )-3-piperidinopropane,

l,2-bis( benzyldithio )-3-piperidinopropane,

l ,2-dimercapto-3-piperidinopropane,

l ,2-bis(ethylthio)-3-pyrrolidinopropane,

1,2-bis( methanesulfonylthio )-3-aziridinylpropane,

l ,2-bis( n-propoxythiocarbonylthio-3-aziridinylpropane,

l,2bis( dimethoxyphosphinothioylthio )-3- thiomorpholinopropane,

l ,2-bis(amidinothio)-3-morpholinopropane dihydrochloride,

l ,2-bis( thiocyanatothio )-3-morpholinopropane,

4-dimethylaminomethyl-2-phenyll ,B-dithiolane,

4-piperidinomethyll ,3-dithiolane-2-thione,

4-diethylaminomethyl-Z-phenyl-l ,3-dithiolane,

4-dicyclohexylaminomethyll ,3-dithiolan-2-one,

3-diethylaminopropanel ,2-bis(sodium thiolsulfate),

l,3-bis( benzylthio )-2-dimethylaminopropane,

l ,3-bis( acetylthio )-2-dimethylaminopropane,

l ,3-bis(diethoxyphosphinothionylthio)-2- dimethylaminopropane,

l ,3-bis( diethoxyphosphinothio )-2-dimethylaminopropane,

1 ,3-dithiocyanate-2-dimethylaminopropane,

I 3-bis( ethoxythiocarbonylthio )-2-dimethylaminopropane,

I ,3-bis(diethylthiocarbamoylthio)-2 dimethylaminopropane,

1 ,3-bis( amidinothio )-2-dimethylaminopropane dihydrochloride,

l ,3-bis(ethyldithio)-2-dimetliylaminopropane,

1 ,3-bis( thiocyanatothio)-2-dimethylaminopropane,

l ,3-bis( benzylsulfonylthio)-2-dimethylaminopropane,

,3-bis( furoylthio)-2-dimethylaminopropane,

-bis( benzyldithio )-2-dimethylaminopropane, -bis(n-propyldithio)-2-dimethylaminopropane, -bis(benzoylthio)-2-dimethylaminopropane,

l -dimercapto-Z-dimethylaminopropane,

l ,3-bis( benzylthio )-2-( 4-dimethylaminobutyl )propane,

1 ,3-bis( benzylthio )-2-diethylaminopropane,

l ,3-bis(benzylthio )-2-piperidinopropane,

l ,3-bis( ethoxythiocarbonylthio)-2-diethylaminopropane,

l ,3-bis( ethylthio)-2-morpholinopropane,

l ,3-bis( ethylthio )-2-piperidinopropane,

l ,3-bis( ethylthio)-2-pyrrolidinylpropane,

1 ,3-bis(methylthio )-2-methylethylarninopropane,

1 3-bis( allylthio )-2-diisopropylaminopropane,

l ,3-bis(n-butylthio)-2-dibutylaminopropane,

1 ,3-bis( Z-methylhexylthio )-3-dicyclohexylaminopropane,

l 3-bis( phenylthio )-2-aziridinylpropane,

1 ,3-bis( benzylthio)-2-thiomorpholinopropane,

l ,3 bis( ethanesulfinylthio Z-di-n-amylaminopropane,

l ,3-bis( benzenesulfonylthio )-2-diphenylaminopropane,

l ,3-bis( ethoxycarbonylthio )-2-phenylmethylaminopropane,

l ,3-bis( propionylthio )-2-phenylethylaminopropane,

1 ,3-bis( chloroacetylthio )-2-diallylaminopropane,

l ,3-bis( p-nitrobenzoylthio)-2-aziridinylpropane,

l ,3-bis( benzylsulfinylthio )-2-dimethylaminopropane,

1 ,3-bis( dimethylcarbamoylthio)-2-pyrroll -ylpropane,

l ,3-bis( phenylamidinothio)-2-pyrrolinl -ylpropane dihydrobromide l,3bis( dimethoxyphosphinothio)-2-diethylaminopropane,

l 3-bis( allyldithio )-Z-di-sec-butylaminopropane,

l ,3-bis( cyclopentyldithio)-2-diallylaminopropa.ne,

l,3-bis( phenyldithio )-2-di-n-propylaminopropane,

l ,3-dimercapto-2-morpholinopropane,

Z-dimethylaminopropane-l ,3-bis( sodium thiolsulfate),

S-dimethylamino-Z-propyl-l ,3-dithiane,

S-methyl-p-tolylamino-l ,3-dithian-2-one,

S-piperidino-Z-phenyl-l ,B-dithiane,

S-dimethylaminol ,3-dithiane-2-thione, etc.

The compounds (I) are relatively strong bases owing to the tertiaryamino group and, in some cases, the amidine or the N- monosubstitutedamidino groups or the carbarnino groups, and form stable acid additionsalts. Those compounds (I) which have thiol groups can form salts with astrong alkali owing to the acid property of the thiol group to form amercaptide. The compounds (I) can be obtained and utilized in the formof acid addition salts or mercaptides as well as in the free form. Theacid which can be used to prepare the acid addition salt is suitablyselected from those which produce, when combined with the compounds (I)in the form of free bases, addition salts whose anions do not lessen thepesticidal properties inherent in the free bases. The strong alkaliwhich can use to prepare the mercaptide is also selected from thosewhich produce, when combined with the thiol compounds among thecompounds (I), mercaptides whose cations do not lessen the pesticidalproperties inherent to the thiol compounds. Appropriate acid additionsalts are, for example, those derived from inorganic acids such ashydrochloric, hydrobromic, hydroiodic, chloric, bromic, iodic,perchloric, perbromic, periodic, sulfuric, nitric, phosphoric andarsenic acids, and from organic acids such as maleic, citric, tartaric,oxalic, benzenesulfonic, toluenesulfonic, ethanesulfonic, picric acidsor those derived from alkylhalides such as methyl iodide, ethyl iodide,etc. Appropriate mercaptides are, for example, those derived from strongalkalis such as sodium hydroxide and potassium hydroxide, or those fromsalts of heavy metals such as lead, copper, zinc or the like.

As briefly stated hereinbefore, the novel compounds thus prepared werefound to show activity for killing lower animals such as insects, mitesor nematodes, but not to show so much toxicity for vertebrates includingmammals and fowls or for plants. Owing to these characteristicproperties, the compounds are used as main components for pesticides,especially for insecticides. 7

When the compounds are brought into practice as pesticides foragricultural and sanitary purposes, the compounds are generallyprocessed so as to fit the intended purposes to form compositions, forexample, wettable powder, solution, emulsifiable solution, dust oraerosol.

For the preparation of the compositions, a variety of adjuvants may beemployed. One or more kinds of the compounds are dissolved or dispersedin an appropriate liquid adjuvant when used as solution, emulsifiablesolution or aerosol. As the liquid adjuvant to be used as solvents, forexample, water, lower alcohols (such as methanol, ethanol, isopropanol,butanol, glycerol or ethylene glycol), ketones (such as acetone, methylethyl ketone, cyclohexanone or cyclopentanone), ethers (such as dioxane,tetrahydrofuran, ethylene glycol monomethyl ether or diethylene glycolmonomethyl ether), aliphatic hydrocarbons (such as n-hexane, gasoline,kerosene, fuel oil, lubricating oil or machine oil); aromatichydrocarbons (such as benzene, toluene, xylene, solvent naphtha ormethyl naphthalene), essential oils, terpenes, chlorinated biphenyl orcottonseed oil can be used. The solvent is often used in a mixture ofthe solvents as exemplified above, since the solvent to be used isdesired to be not only excellent in its solubility but also less toxicfor plants or human bodies.

For perparing dust composition of the compounds, there are usuallyemployed dust diluents or carriers. One or more kinds of the compoundsare finely pulverized, for example, in a ball mill, edge runner orimpact pulverized, and the thus pulverized compounds are admixed withdust diluents or carriers. As the diluents or the carriers, for example,vegetable powder (such as soybean flour, wheat flour, tobacco powder,walnut flour or saw dust), clay (such as kaolin, kaolinite, saponite,vermiculite, beidellite, montmorillonite -bentonite or Fuller's earthorattapulgite), talc, pyrophyllite, calcium lime, magnesium lime,diatomaceous earth, silica, hydroxyapatite, calcium carbonate, dolomite,calcite, calcium sulfate, hydrated alumina, carbon black or sulphur canbe used.

Another kind of adjuvant is surface active agent which is used assticking or developing agent, emulsifier, or solubilizer for improvingthe effect or the stability of compositions. Among commerciallyavailable surface active agents, salts of sulfonated castor oil, saltsof alkyl aryl sulfonates or non-ionic surfactants such aspolyoxyethylene diaryl ether, polyoxyethylene alkyl aryl ether andpolyoxyethylene sorbitan monoacylate (the acyl group having 10 to 18carbon atoms) are preferably used as emulsifying and solubilizing agentsfor the compositions of the present invention.

The pesticidal compositions of the present invention may contain otherpesticides (such as benzenehexachloride( BHC),dichlorodiphenyltrichloroethane (DDT), aldrin, dieldrin, endrin,pyrethrin, rotenone, parathion or the other organic phosphorus poisons),acaricides, nematocides, fungicides, herbicides, attractants orrepellents. They may also contain growth hormones, fertilizers, orperfumes, all these additions being considered the adjuvants in thecompositions of the instant invention.

The compounds (I) or compositions thereof of the present invention wereobserved to have the effect to kill a wide variety of insects, mites andnematodes, and exterminate those harmful animals as exemplified below orat least lessen remarkably the number of surviving animals: The examplesof plant feeding insects etc. are:

Colorado potato beetle (Leptinotarsa decemilineata),

Large 28-spotted lady beetle (Epilachna vigintioctomaculata),

28-spotted lady beetle Epilachna sparsa orientalis),

Striped flea beetle (Phyllotreta striolata),

Cucurbit leaf beetle (Aulacophora femoralis, adult),

Grape leaf beetle (Acrothinium gackkwittchii, adult),

Red bean beetle (Callosobruchus chinensis),

German cockroach (Blattela germanica),

Rice leaf beetle (Lema oryzae),

House fly Musca domestica),

Cabbage sawfly (Athalia rosae japonensis, larva) Rice stem borer (Chilosuppressalis),

Tobacco cutworrn Prodenia litura),

Rice plant skipper (Parnara guttata, larva) Rice green caterpillar(Naranga aenescens, larva),

Cabbage armyworm (Barathra brassicae, larva) Giant bagworm Cryptotheleaformosicola, larva),

Pea bagworm (Cryptothelea minuscula, larvae),

Pale clouded yellow (Colias hyale poliographus, larvae),

Cabbage worm (Pieris rapae, larva),

Citrus red mite (Tetranychus citri),

Soybean aphid (Aphis glycines),

Tumip aphid (Rhapalosiphum pseudobrassicae),

Two-spitted mite (Tetranychus bimaculatus), etc.

Compositions for direct application to vegetation may c0nrain from 0.1to 10 percent or more of the compound(s) (l) by weight. When thecomposition is designed as a concentrate for preparation of sprays ormore dilute dusts, the contents of the compound(s) (I) may vary from 10to percent weight.

The pesticidal activity of the compounds (I) is illustrated withreference to a typical representative of experiments.

EXPERIMENT 1.

An emulsion of the test compound illustrated in Table I was sprayed oversoybean plants infested with soybean aphids (A- phis glycines) or overkidney bean plants on which twospotted mites (Tetranychus bimaculatus)are kept, the plants being cultivated on a tum-table. After 48 hours,the number of surviving soybean aphids or two-spotted mites was countedto calculate the survival rate. The emulsions used were prepared bydissolving 10 parts by weight of the test compounds in parts by volumeof 50 percent aqueous ethanol mixture containing 20 parts by volume ofsorbitan laurate polyoxyethylene ether (Tween 20), and by diluting thesolution with tap water so as to the concentration of the test compoundto 0.2 percent. The figures in Table 1 are mean values of three to sixdata obtained by experiments carried out parallelly.

TABLE 1 Survival rates(%) Test Compound Soybean aphids Two-spotted miteshydrogen oxalate 33.3 Control (Tap water) 1 12.0 81.7

EXPERIMENT 2.

The test compounds were dissolved in tap water containing 0.02 percentof a sticking agent, so as to adjust the concentration of the testcompound as illustrated in Table 2. As the sticking agent, thecomposition consisting of 20 percent of alkylphenol polyethylene glycolether, 12 percent of lignin sulfonic acid and 68 percent of aqueousmethanol was added. Young leaves of Chinese cabbage were immersed in thethus prepared test solution for several seconds and the wet leaves wereallowed to stand in air until the surface of the leaves dried. Theleaves thus treated were placed in the pots of 9 centimeters in diameterand 3 centimeters in height. Test insects, i.e. cabbage wom-is (Pierisrapae, larvae) or striped flea beetles (Phyllotreta striolata, adults),were set free on the leaves. After 24 hours, the number of killedinsects were respectively counted. Results are shown in Table 2.

compound used compound used l,3-Bis( propyldithio)-2-dimethylaminopropane hydrogen oxalate The test compounds weredissolved in the water containing 0.05 percent of the sticking agent asused in Experiment 2, so as to adjust the concentration of the testcompound as illustrated in Table 3. Rice plants growing onIISOOO-are-Wagnerpot were sprayed with 10 cubic centimeters per pot ofthe above-prepared solution. Matured eggs of rice stem borer (Chilosuppressalis) were placed on the thus-sprayed rice plants. After a weekfrom when the larvae had entered into the stems, the stems were cut opento count the number of surviving larvae.

TABLE 3 test compound concentration of average of survival testcompound(%) rates of larvae l,3-Bis( propyldithio)-2-dimethylaminopropane 0.025 33.1

hydrogen oxalate 0.05 30.0

4,9-Bis( dimethylamino 1 ,2,6,7-

tetrathiecane dihydrogen 0.025 0.0

dioxalate 0.05 0.0

Control 64.2

EXPERIMENT 4 The test compounds were dissolved in water containingsorbitan laurate polyoxyethylene ether in an amount of twice as much asthe test compounds. Leaves of radish were immersed in the thus-preparedsolution and the wet leaves were allowed to stand in air until thesurface of leaves dried. The leaves thus treated were placed in glasspots. Twenty larvae of Daikon" leaf beetles (Phaedon brassicae) were setfree in each pot. After 48 hours, the number of killed insects wascounted to calculate mortality. The figure of mortality in Table 4 isthe average value of data obtained by duplicate trials.

EXPERIMENT 5 The droplets from 1 ml. of pipetted aqueous solution of thetest compounds were dropped into a Petri dish until the droplets coveredhomogeneously the bottom of the dish. After the droplets were dried byairing gently, red bean beetles (Callosobruchus chinensis) were set freein the Petri dish. 24 Hours later, the number of killed insects wascounted to calculate the lethal concentration (LC,,.,).

Test compound Lethal concentration LCM?) l,3-Bis( propyldithio )-2-dimethylaminopropane hydrogen oxalate I,B-Dimercapto-2-dimethylaminopropane hydrogen oxalate 1 B-Dimercapto-2-dimethylaminopropane disodium salt 4,9-Bis( dimethylamino l,2,6,7-tetrathiecane dihydrogen dioxalate l ,2-Bis( acetylthio3-dimethylaminopropane hydrogen oxalate S-Dimethylaminol.3-dithiane-2-thione l ,2-Dimercapto-3-dimethylaminopropane hydrogenoxalate l ,3Dit.hiocyanato-2-dimethylaminopropane hydrogen oxalate l,3-Bis(ethoxy-thiocarbonylthio)-2- dimethylaminopropane hydrogen oxalatel,3-Bis( amidinothio)-2- dimethylaminopropane hydrogen oxalatedihydrochloride l ,3-Bis( ethyldithio )-2-dimethylaminopropane hydrogenoxalate l ,3-Bis( acetylthio)-2-dimethyla.minopropane hydrogen oxalateEXPERIMENT 6 The test compounds were dissolved in water containing 0.1percent of the same sticking agent as used in Experiment 2. When thetest compounds were free bases the aqueous solution was adjusted to pH8.5 with phosphoric acid buffer solution. Twenty milliliters each perpot of the solution thus prepared were sprayed from the distance ofcentimeters with the pressure of lkgJcrn". Survival rate was calculatedafter 2 or 4 days to obtain the result shown in Table 6.

TABLE 6 Survival rate (percent) Concentration of the Soybean aphidsTwo-spotted mites test com a pound 2 days 4 days 2 days 4 days Testcompound (percent) after after after after 4,9-bls(d)itpc2thylamino,6,7- tetrnthiecano 632 ""5 4,D-bis(dimnthylamlno)-1,2,6,7-tetrathlecane dlhydrogen dloxalate 0. 05 0. 4 2. 64-d1m0thylamlnomethyl-1,3- dithlolaneth lone 0. 025 58. 9 1 ,3-bis(ethyldithlgO-Z-dlmethylam nopropane hydrogen Oxalate-l 092132 1313 19:2 31?1:311:11: Control (malathlorl) O. 025 10%. 4 {S n0. 0 .7 9 1. 9 14 .3cmtml 0 1 129.4 154. a

{Malathion=0,0-dimethy1 S-(1,2-dicarbethoxyethyl) phosphodithioa e. if Vg EXPERIMENT 7.

(tuna Test on Acute toxicity to mice (F -race) in intraperitoneal nje n:Dose Killed/ Test compound (mg/kg. Used l,2-Bis( propyldithio)-2-dimethylarnino- 100 [/3 propane hydrogen oxalate 200 3/3 500 3/34-Dimethylaminomethyl- 1 ,3-

dithiolane- 1 0/3 2-thione 200 3/3 500 3/3 The following examples setforth presently preferred il1ustrative typical compounds represented bythe formulas (I) of the invention and of the procedure for theirpreparation, and will serve to make apparent the compounds embraced bythe fonnulas (l) and their preparation respectively. Pesticidalcompositions fit for practical purposes are also described by means ofexemplary compositions. it will be understood, of course, that theinvention is not limited to the particular details of these examples orexemplary compositions since 'they are no more than examples of somepreferred embodiments of the invention. In these examples are exemplarycompositions, temperatures are uncorrected and shown in degreescentigrade. The abbreviation ml. means millileter or millileters," andrespective amounts of materials shown by either of part(s)" or are onweight basis.

EXAMPLE 1.

In 50 ml. of ethanol was neutralized 3.4 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride with 0.9 gram of potassiumhydroxide. The solution was gradually dropped into a mixture of 4.9grams of sodium benzyl mercaptide and 20 ml. of ethanol with stirring atroom temperature. After the addition, the mixture was warmed for alittle while to To a solution of 17.3 grams of 1,2-bis (benzy1thio)-3-piperidinopropane in 100 cubic centimeters of ether was added anethereal solution of oxalic acid to give 17.5 grams ofl,2-bis(benzylthio)-3-piperidinopropane hydrogen oxalate as white andpowdery crystals melting at 126-129 recrystallized from isopropanol.

EXAMPLE 3.

In a mixture of 100 ml. each of ethanol and methanol was dissolved 54.4grams of 1,2-dichloro-B-diethylaminopropane hydrochloride. A mixture of14 grams of potassium hydroxide and 150 m1. of ethanol was added to theabove-prepared solution under ice-cooling, whereupon potassium chlorideseparated and was filtered off under suction. A mixture prepared from11.5 grams of metallic sodium, 62.1 grams of benzyl mercaptan 100 ml. ofethanol was added to the aboveprepared filtrate and the mixture wasrefluxed on water bath with stirring for 2 hours, whereupon sodiumchloride separated and filtered off with suction. The filtrate wasconcentrated under reduced pressure to dryness and the residue wasdissolved in ether. The ethereal solution was washed with water, driedand concentrated to dryness to give 67.3 grams of 1,2-bis( benzylthio)--diethylaminopropane as brown oil.

EXAMPLE 4.

In 150 ml. of ethanol was neutralized 4.8 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride with 1.4 grams ofpotassium hydroxide. To the solution was added gradually 5.2 grams ofpotassium thiolacetate under agitation at room temperature. After theaddition, the mixture was warmed for a little while to separate outpotassium chloride, which was then filtered off. The filtrate wasconcentrated under reduced pressure to leave an oily substance, whichwas extracted with ether. The ethereal solution was washed with water,dried on anhydrous sodium sulfate and warmed to distilled off the etherto leave an oily substance. The oily residue was dissolved in dry etherand an ethereal solution saturated with anhydrous oxalic acid was addedgradually to the ethereal solution to separate out crystals, which wererecrystallized from a mixture of ethanol and ether to obtain1,3-bis(acetylthio)-2-dimethy1aminopropane hydrogen oxalate as colorlesscrystals melting at 91-94.

EXAMPLE 5.

A solution of 12.5 grams of 1,2-dichloro-3- dimethylaminopropanehydrochloride in 100 ml. of ethanol was neutralized with 3.6 grams ofpotassium hydroxide, whereupon potassium chloride separated and wasfiltered. To

separate out sodium chloride, which was then filtered oftZThe, th fil ewas dded an tha olic solution of sodium filtrate was concentrated underreduced pressure to leave an oily substance, which was extracted withether. The ethereal solution was washed with water and dried overanhydrous sodium sulfate. An ethereal solution saturated with anhydrousoxalic acid was gradually added to the dried ethereal solution toseparate out crystals, which were collected by filtration, decolorizedand recrystallized from a mixture of ethanol and ether to give 4.5 gramsof l,3-bis(benzylthio)-2- dimethylaminopropane hydrogen oxalate ascolorless crystals melting at l32135.

EXAMPLE 2.

To a solution of 18.1 grams of 1,2-dichloro-3- piperidinopropanehydrochloride in a mixture of 50 ml. each of ethanol and methanol, therewas added a solution of 4.4 grams of potassium hydroxide in 50 m1. ofethanol under icecooling with stirring, whereupon potassium chlorideseparated and was filtered off with suction. A mixture prepared from 3.6grams of metallic sodium, 19.5 grams of benzyl mercaptan and. 50 ml. ofethanol was added to the above-obtained filtrate and the mixture wasrefluxed on water bath with stirring for 2 hours. The sodium chlorideseparating therein was filtered off with suction and the filtrate wasconcentrated under reduced pressure to dryness to give oily residue,which was dissolved in ether. The ethereal solution was washed withwater and dried. Ether was then evaporated to give 23.1 grams of 1,2-bis(benzylthio)-3-piperidinopropane as brown oil.

thiolacetate which had been prepared from 9.9 grams of thiolacetic acid,3 grams of metallic sodium and 100 ml. of ethanol. The mixture wasallowed to stand overnight and was refluxed on the water bath for 40minutes, whereupon sodium chloride separated and was filtered off. Thefiltrate was concentrated under reduced pressure to dryness and the oilyresidue was dissolved in ether. The ethereal solution was washed withwater, and dehydrated. An ethereal solution saturated with anhydrousoxalic acid was added dropwise to the dehydrated ethereal solution toseparate crystals, which were collected by filtration to obtain 6 gramsof 1,2-bis( acetylthio)- 3-dimethylaminopropane hydrogen oxalate, whichdecomposes at about 105115. The crude crystals were recrystallized frommethanol to give pale yellow crystals decompositing at l24128.

EXAMPLE 6.

A solution of 9.6 grams of 1,2-dichloro-3- dimethylaminopropanehydrochloride in 50 ml. of ethanol was neutralized with 2.8 grams ofpotassium hydroxide, whereupon potassium chloride separated and wasfiltered off. To the filtrate, there was added a solution of 8.2 gramsof sodium trithiocarbonate in 50 ml. of ethanol and the mixture wasrefluxed on a water bath for 1 hour. After cooling, sodium chlorideseparated, was filtered off and the filtrate was concentrated underreduced pressure. To the residue, there was added 100 ml. of water andextracted three times with 50 ml. each of ether. All ethereal extractswere combined and dehydrated, after which a solution of 7.5 grams ofanhydrous oxalic acid in 100 ml. of ether was added to separate 8.2grams of crude 4-dimethylaminomethyl-1,3-dithiolane-2-thione hydrogenoxalate, which decomposes at about l58168. The crude crystals wererecrystallized from aqueous ethanol to give yellow plates decomposing at187189.

EXAMPLE 7.

Eighty grams of gaseous ammonia was dissolved in 1.2 liters of anhydrousmethanol under cooling and then hydrogen sulfide was saturated therein.To the solution was added 80 grams of l,2-dibromo-B-dimethylaminopropane hydrochloride and the mixture wasallowed to stand overnight in a sealed vessel at room temperature. Then,the mixture was boiled for 2 days, while introducing hydrogen sulfidetherein. Resulting crystals were filtered E and the filtrate wasconcentrated under reduced pressure to leave an oily residue, which wasfurther distilled to obtain 6.0 grams of 1,2-dimercapto-3-dimethylaminopropane, boiling at 7 l-78/5 mmHg.

EXAMPLE 8.

In 50 ml. of anhydrous ethanol, there was neutralized 7.9 grams of l,3-dichloro-2-dimethylaminopropane hydrochloride with 2.2 grams ofpotassium hydroxide to give the free amine. To the solution was added asolution of 6.1 grams of ammonium thiocyanate in 100 ml. of anhydrousethanol and the mixture was agitated for 2 days at room temperature.After the resulting precipitate had been filtered ofi, the filtrate wasconcentrated under reduced pressure to leave an oily substance, whichwas dissolved in ether. The ethereal solution was washed with water anddried. An anhydrous oxalic acid solution in ether was added to the driedethereal solution to separate crystals, which were collected andrecrystallized from a mixture of ethanol and ether to give 7.4 grams ofl,3-dithiocyanato-Z-dimethylaminopropane hydrogen oxalate, melting atl23l 24 with decomposition.

EXAMPLE 9.

In 50 ml. of anhydrous ethanol was neutralized 7.9 grams ofl,3-dichloro-Z-dimethylaminopropane hydrochloride with 2.2 grams ofpotassium hydroxide to give free amine. The free amine was added to asolution of 12.8 grams of potassium ethylxanthogenate in 150ml. ofanhydrous ethanol and the mixture was stirred for 2 days at roomtemperature. The resulting reaction mixture was treated in a similarmanner to the preceding example to give 2.9 grams of1,3-bis(ethoxythiocarbonylthio)-2-dimethylaminopropane hydrogen oxalate,melting at 1 l-l 16 with decomposition.

EXAMPLE 10.

In 50 ml. of anhydrous ethanol was neutralized 4.9 grams of1,3-dichloro-2-dimethylaminopropane hydrochloride with 1.4 grams ofpotassium hydroxide to give the free amine. The free amine was added toa solution of 8.6 grams of sodium N,N- diethyldithiocarbamate in 150 ml.of anhydrous ethanol and the mixture was stirred for 2 days at roomtemperature. The resulting reaction mixture was treated in a similarmanner to the preceding example. The obtained crystals wererecrystallized from ethanol to give 2.9 grams of l,3-bis(N,N-diethylthiocarbamoylthio)-2-dimethylaminopropane hydrogen oxalate,melting at 1 l8-l with decomposition.

EXAMPLE 1 l.

in 50 ml. of anhydrous ethanol was neutralized 7.9 grams ofl,3-dichloro-Z-dimethylaminopropane hydrochloride with 2.2 grams ofpotassium hydroxide to give the free amine. The free amine was added toa solution of 6.1 grams of thiourea in 100 ml. of anhydrous ethanol andthe mixture was stirred for 2 days at room temperature. The resultingreaction mixture was treated in a similar manner to the precedingexample to give 2.8 grams of l,3-bis(amidinothio)-2-dimethylaminopropanehydrogen oxalate dihydrochloride, melting at l06l08 with decomposition.

EXAMPLE 12.

In 100 ml. of 50 percent aqueous ethanol was neutralized 9.6 grams of l,3-dichloro-2-dimethylaminopropane hydrochloride with 2.0 grams ofsodium hydroxide to give the free amine, and 24.8 grams of sodiumthiosulfate was added thereto. The mixture was heated for a littlewhile, and concentrated under reduced pressure to leave a pale brownoily substance.

On the other hand, 62 grams of ethyl mercaptan was dissolved in 50 ml.of 2-normal aqueous sodium hydroxide solution and the solution wassaturated with sodium chloride. The above-obtained oily substance wasgradually added to the above-prepared solution. After being kept at roomtemperature for about 5 to 6 hours, the mixture was extracted twice withether. The ethereal solutions were combined, washed with water anddried.

An anhydrous oxalic acid solution in ether was added to the driedethereal solution to separate crystals, which were collected andrecrystallized from a mixture of ethanol and ether to give 2.2 grams of1,3-bis(ethyldithio )-2- dimethylaminopropane hydrogen oxalate meltingat ll3l 15 with decomposition.

EXAMPLE 13.

A mixture of 24 grams of sodium sulfide and 32 grams of sulfur powderwas warmed on the water bath to give a uniform solution colored in redorange, and 375 ml. of water and 15 grams of anhydrous potassiumcarbonate were added thereto. The mixture was cooled with a freezingmixture. A solution of 15 grams of l ,3-dichloro-2-dimethylaminopropanehydrochloride in 75 ml. of water was gradually dropped into the cooledmixture with stirring, during which the reaction temperature was kept ata temperature from 2 to 3. After the addition, the reaction mixture wasallowed to stand at 2 to 3 in a refrigerator for 2 days. Then, at roomtemperature, 50 ml. of 6-normal aqueous sodium hydroxide solution and0.25 gram of potassium cyanate were added to the reaction mixture andthe resulting mixture was extracted twice with chloroform. The extractwas treated in a similar manner to the preceding example to give 4.2grams of 4,9- bis(dimethylamino)-l,2,6,7-tetrathiocane dihydrogendioxalate melting at l51-l54 with decomposition.

EXAMPLE 14.

In 50 ml. of anhydrous ethanol 7.9 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride were changed into the free base with2.2 grams of potassium hydroxide. The resulting free amine was added tothe solution of sodium 0,0- diethylphosphorodithioate, which had beenprepared from 15.1 grams of 0,0-diethylphosphorodithioic acid and thesodium alcoholate solution prepared from 1.8 grams of metallic sodiumand 100 ml. of ethanol, and the mixture was agitated for 2 days at roomtemperature. Crystallizing sodium chloride was filtered off and thefiltrate was concentrated to leave an oily substance. The residue wasdissolved in ether and the ethereal solution was washed and dehydrated.To the dried ethereal solution was added 5 percent ethereal solution ofanhydrous oxalic acid to crystallize the objective compound, which wasfiltered and recrystallized from a mixture of ethanol and ether to give8.6 grams of 1,3-bis(diethoxyphosphinothioylthio)-2-dimethylaminopropanehydrogen oxalate, melting at -82 with decomposition.

The same procedure as mentioned above was brought about except that 14.5grams of 0,0-diethylphosphorothiolic acid was used in place of 15.1grams of 0,0- diethylphosphorodithiolic acid, whereupon 1,3-bis(diethoxyphosphinothio)-2-dimethylaminopropane hydrogen oxalate wasobtained.

A mixture of 15 grams of l,3-bis(benzylthio)-2- chloropropane and 45 ml.of 31 percent solution of dimethylamine in benzene was placed in apressure vessel and heated at 160 for 16 hours. After cooling, resultantdimethylamine hydrochloride was filtered off and the filtrate wasconcentrated under reduced pressure to dryness. The residue wasdissolved in a small amount of water and extracted with 50 ml. of ether,and the ethereal solution was dried over anhydrous sodium sulfate. Tothe ethereal extract, an ethereal solution saturated with oxalic acidwas added until no more precipitate settled. The precipitates werecollected and recrystallized to give 1 1 grams of l,3-bis(benzylthio)-2-dimethylaminopropane hydrogen oxalate, melting at l32-l3 5.

EXAMPLE 16 A mixture of 7.5 grams of crude l,3-dibenzylthio-2-chloropropane and 24 ml. of 33 percent solution of diethylamine inbenzene was placed in a pressure vessel and heated at 160 for 14 hours.After cooling, resulting diethylamine hydrochloride was filtered ofi andthe filtrate was concentrated under reduced pressure to dryness. A smallamount of water and 20 cubic centimeters of ether were added to theresidue and an ethereal solution saturated with oxalic acid was addedthereto until no more precipitate arose. The precipitates were collectedand recrystallized to give 5.5 grams of l,3-bis(benzylthio)-2-diethyla.minopropane hydrogen oxalate, melting atl35-l42.

EXAMPLE 17.

A mixture of 15 grams of l,3-bis(ethoxythiocarbonylthio)- 2-bromopropaneand 45 ml. of 33 percent solution of diethylamine in benzene was heatedon water bath for 3 hours. After cooling, resultant inorganic salts wereremoved by filtration and the filtrate was concentrated under reducedpressure to dryness. The residue was dissolved in diluted acetic acidand the solution was extracted with ethyl acetate to remove theimpurities soluble in the solvent. The aqueous layer was adjusted to pH9.0 with sodium carbonate and extracted twice with 50 ml. each of ether.An ethereal solution saturated with oxalic acid was added to theethereal extacts until no more precipitate settled. The precipitateswere collected and recrystallized to give l.5 grams ofl,3-bis(ethoxythiocarbonythio)-2-diethylaminopropane hydrogen oxalate.

EXAMPLE 18.

Five grams of l,3-bis(ethylthio)-2-chloropropane and grams of morpholinewere heated in 50 ml. of toluene for 7 hours under reflux. Aftercooling, resulting crystals were filtered off and the filtrate wasconcentrated under reduced pressure to dryness. The oily residue wasdissolved in ether. The ethereal solution was washed with water anddried. An ethereal solution saturated with oxalic acid was added to thedried ethereal solution until no more precipitate settled. Theprecipitates were collected and recrystallized from acetone to give 4.7grams of l,3-bis(ethylthio)-2-morpholin0propane hydrogen oxalate ascolorless crystals melting at l2ll23.

EXAMPLE 19.

Five grams of l,3-bis(ethylthio)-2-chloropropane and 20 grams ofpiperidine were heated in 50 ml. of toluene under reflux for 10 hours.After cooling, resultant crystals were filtered off and the filtrate wasconcentrated under reduced pressure to dryness. The oily residue wasdissolved in ether and the ethereal solution was washed with water anddehydrated. An ethereal solution saturated with oxalic acid was added tothe dehydrated ethereal solution until no more precipitate settled. Theprecipitates were collected and recrystallized to give 3.2 grams ofl,3-bis(ethylthio)-2- piperidinopropane hydrogen oxalate, melting atl20l 24.

18 EXAMPLE 20.

Five grams of 1,3-bis(ethylthio)-2-chloropropane and 20 grams ofpyrrolidine was heated in 50 ml. of benzene under reflux for 14 hours.After cooling, resulting crystals were filtered off and the filtrate wastreated in the same manner as in the preceding example to obtain 3.5grams of 1,3- bis( ethylthio)-2-pyrrolidinopropane hydrogen oxalatemelting at l 10-l 13.

EXAMPLE 21.

A mixture of 10 grams of l,3-bis(benzylthio) propan-Z-one, 70 ml. ofdimethylformamide and 70 ml. of percent formic acid was placed in avessel equipped with the apparatus for dehydration and was heated on oilbath at 180 for 10 hours. The reaction mixture was concentrated underreduced pressure and the residue was extracted with ether. The etherealextract was extracted with 5 percent hydrochloric acid to collect amineproduct. The aqueous layer was alkalified with diluted aqueous solutionof sodium hydroxide and extracted with ether. The ethereal solution waswashed with water, dried over sodium sulfate and concentrated to drynessto give crude 1,3- bis(benzylthio)-2-dimethylaminopropane, which wasdissolved in ether and the solution was shaken together with an aqueoussolution of oxalic acid to give 1.5 grams of the corresponding hydrogenoxalate melting at l32-l 35.

EXAMPLE 22.

Ten grams of 2-phenyl-5-hydroxy-l ,3-dithiane was dissolved in a mixtureof 45 ml. of benzene and 2 ml. of pyridine. Twenty milliliters ofthionyl chloride was added to the solution under ice-cooling withstirring, and the reaction was brought about for 2 hours at roomtemperature. The reaction mixture was poured into ice-water. The aqueousmixture was extracted with ether. The ethereal solution was dehydratedand concentrated to give 9.5 grams of 2-pheny1-5-chlorol ,3-dithiane.

The compound thus obtained was dissolved in 50 ml. of benzene. Thesolution was mixed with 20 ml. of 32 percent dimethylformamide inbenzene, and the mixture was heated at for 16 hours in an autoclave. Thereaction mixture was concentrated and the concentrate was extracted withether. An ethereal solution saturated with oxalic acid was addedto theethereal extract to crystallize the objective compound, which wasfiltered and recrystallized from a mixture of ethanol and ether to give4.0 grams of 2-phenyl-5-dimethylaminol ,3- dithiane hydrogen oxalate,melting at l41-l43 with decomposition.

EXAMPLE 23.

Nine and half grams of 2-phenyl-4-hydroxymethyl-1,3- dithiolane wasallowed to react with thionyl chloride in a similar way to the procedurein the preceding example to give 2-phenyl-4-chloromethyll 3-dithiolane.

The compound was allowed to react with dimethylamine in benzene at 160for 16 hours in an autoclave to give 4.0 grams of2-phenyl-4-dimethylaminomethyl-1,3-dithiolane, which was recrystallizedas the hydrogen oxalate to melt at 132 with decomposition.

EXAMPLE 24.

A mixture of 40 ml. of anhydrous ethanol and 80 ml. of liquid ammoniawas cooled with dryice. A solution of 4.9 grams ofl,3-bis(benzylthio)-2-dimethylaminopropane in 40 ml. of anhydrousethanol and L9 grams of metallic sodium were alternatively added to thecooled mixture under agitation, and agitation was further continued for30 minutes. Then, anunonia and ethanol were distilled off and 50 ml. ofwater was added to the residue. The aqueous mixture was extracted withether to remove impurities soluble in ether. The aqueous layer wasadjusted to pH 9.0 by the addition of hydrochloric acid and saturatedwith sodium chloride. A solution of 6 grams of sodium benzylthiolsulfatein 20 ml. of water was dropped into the above-prepared solution underagitation, whereupon an oily substance separated, which was extractedwith ether. The ethereal extract was mixed with 25 ml. of 7 percentaqueous oxalic acid solution; the mixture was vigorously shaken andallowed to stand overnight to obtain 2.1 grams ofl,3-bis(benzyldithio)-2-dimethylaminopropane hydrogen oxalate ascolorless crystals melting at l l 5-l 19.

EXAMPLE 25.

l,3-Dimercapto-2-dimethylaminopropane, which had been prepared from 4.9grams of l,3-bis(benzylthio )-2-dimethyl aminopropane in the same manneras in the preceding example, was dissolved in 50 ml. of water and theaqueous solution was adjusted to pH 9.0with the addition of hydrochloricacid and saturated with sodium chloride. A solution of 20 grams ofsodium propylthiolsulfate in 25 ml. of water was added to the aqueoussolution saturated with sodium chloride, whereupon an oily substanceseparated, which was extracted with 80 ml. of ether. The etherealextract was mixed with 25 ml. of 7 percent aqueous oxalic acid solution.The mixture was shaken and allowed to stand overnight to obtain 1.5grams of 1,3- bis(propyldithio)-2-dimethylaminopropane hydrogen oxalateas colorless crystals melting at l30-l 34.

EXAMPLE 26.

A solution of 3 grams of 1,2-dimercapto-3- dimethylaminopropane in 30ml. of water was adjusted pH 9.0 with 10 percent aqueous sodiumhydroxide solution and saturated with sodium chloride. A solution of 6grams of sodium benzylthiolsulfate in 20 ml. of water was added to thesolution saturated with sodium chloride under agitation, whereupon anoily substance separated, which was extracted three times with 30 ml.each of ether. The ethereal extacts were combined and mixed with 25 ml.of 7 percent aqueous oxalic acid solution. The mixture was shaken andallowed to stand ovemight to allow the objective compound tocrystallize, which was filtered and recrystallized to obtain 2 grams ofl,2-bis(benzyldithio)-3-dimethylaminopropane hydrogen oxalate ascolorless crystals melting at 1 EXAMPLE 27.

A solution of 3 grams of 1,2-dimercapto-3-dimethylaminopropane-1,2-dithiol in 30 ml. of water was adjusted to pH9.0 with 10 percent aqueous sodium hydroxide solution and saturated withsodium chloride. A solution of grams of sodium propylthiolsulfate in 20ml. of water was added to the solution saturated with sodium chloride,whereupon an oily substance separated, which was extracted three timeswith 30 ml. each of ether. The ethereal extracts were combined and mixedwith ml. of 7 percent aqueous oxalic acid solution. The mixture wasshaken and allowed to stand overnight to crystallize the objectivecompound, which was filtered and recrystallized to obtain 1.5 grams of1,2-bis(propyl dithio)-3-dimethylaminopropane hydrogen oxalate ascolorless crystals melting at 128-l 32.

EXAMPLE 28.

A mixture of 40 ml. of anhydrous ethanol and 80 ml. of liquid ammoniawas cooled with dry-ice. A solution of 4.6 grams of1,3-bis(benzylthio)-2-dimethylaminopropane in 40 ml. of anhydrousethanol and 1.9 grams of metallic sodium were alternatively added to thecooled mixture with stirring to allow the reaction to take place. Afterthe reaction ended, ammonia and ethanol were distilled ofi. The oilyresidue was dissolved in 50 ml. of water and the solution was extractedwith ether to remove oily substances insoluble in water. The aqueouslayer was separated and 6.2 grams of benzoyl chloride was dropped intothe separated solution under ice-cooling and agitation. After minutesfrom the end of the addition, oily substance separating was extractedwith 80 ml. of ether. The ethereal extract was mixed with 25 ml. of 7percent aqueous nun solution of oxalic acid. The mixture was shaken andallowed to stand overnight, whereupon the objective compoundcrystallized, which was filtered and dried to give 2.] grams of 1,3-bis(benzoylthio)-2-dimethylaminopropane hydrogen oxalate as whiteleaflet crystals melting at l54-l 56.

EXAMPLE 29.

1,3-Dimercapto-Z-dimethylaminopropane, which had been prepared from 4.6grams of 1,3-bis(benzylthio)-2- dimethylaminopropane in the same manneras in the preceding example, was dissolved in 50 ml. of water, and 6.5grams of furoyl chloride was dropped into the aqueous solution. After 30minutes from the end of the addition, oily substance separating wasextracted with ml. of ether. The ethereal extract was mixed with 25 ml.of 7 percent aqueous solution of oxalic acid. The mixture was shaken andallowed to stand overnight, whereupon the objective compoundcrystallized, which was filtered and dried to give 2.5 grams of1,3-bis(furoylthio)-2-dimethylaminopropane hydrogen oxalate as whitecrystals melting at 152158.

EXAMPLE 30.

into a solution of 2.1 grams of 1,2-dimercapto-3- dimethylaminopropaneand 3.2 grams of sodium hydroxide in 50 ml. of water was dropped 6.2grams of benzoyl chloride under ice-cooling and agitation. After 30minutes from the end of the addition, oily substance separating wasextracted with 80 ml. of ether. The ethereal extract was mixed with 25ml. of 7 percent aqueous solution of oxalic acid. The mixture was shakenand allowed to stand overnight, whereupon the objective compoundcrystallized, which was filtered and dried to obtain 2.1 grams ofl,2-bis(benzoylthio )-3- dimethylaminopropane hydrogen oxalate as whiteleaflet crystals melting at 1 54 l 56.

EXAMPLE 31.

into a solution of 2.1 grams of 1,2-dimercapto-3- dimethylaminopropaneand 3.2 grams of sodium hydroxide in 50 ml. of water was dropped 6.5grams of furoyl chloride under ice-cooling and agitation. After 30minutes from the end of the addition, oily substance separating wasextracted with 80 m1. of ether. The ethereal extract was mixed with 25ml. of 7 percent aqueous solution of oxalic acid. The mixture was shakenand allowed to stand overnight, whereupon the objective compoundcrystallized, which was filtered and dried to give 2.5 grams ofl,2-bis(furoylthio)-3- dimethylaminopropane hydrogen oxalate as whitecrystals melting at l52158.

EXAMPLE 32.

A solution of 2.7 grams of 1,2-dimercapto-3- dimethylaminopropane and4.2 grams of sodium hydroxide in 70 ml. of water was saturated withsodium chloride, and 8 grams of acetic anhydride was dropped into theaqueous solution under ice-cooling and agitation. Then, after adding 80ml. of ether thereto, the mixture was agitated for additional 30minutes. The ether layer was separated, dried and mixed with theethereal solution saturated with oxalic acid. The mixture was shaken andallowed to stand overnight, whereupon the objective compoundcrystallized, which was filtered and dried to obtain 5 grams of l,2-bis(acety1thio )-3- dimethylaminopropane hydrogen oxalate as whitepowdery crystals melting at 1 l5-1 16C.

EXAMPLE 33.

A mixture of 40 ml. of anhydrous ethanol and 80 ml. of liquid ammoniawas cooled with dry-ice. A solution of 4.9 grams ofl,3-bis(benzylthio)-2-dimethylarninopropane in 40 ml. of anhydrousethanol and 1.9 grams of metallic sodium were alternately added to thecooled mixture. After the mixture was agitated for 30 minutes, ethanoland ammonia were distilled ofi to leave 3.6 grams of crude1,3-dimercapto-2- dimethylaminopropane.

The crude product was dissolved in water. The solution was neutralizedwith hydrochloric acid, saturated with sodium chloride and extractedseveral times with ethyl acetate. The ethyl acetate extracts werecombined, dehydrated and concentrated under reduced pressure to give 2.3grams of further purified l,3-dimercapto-2-dimethylaminopropane.

EXAMPLE 34.

One gram of 4-dimethylaminomethyl-Z-phenyl-l,3- dithiolane was dissolvedin a mixture of 20 ml. of ether and 50 ml. of liquid ammonia. To thesolution under agitation was added 0.5 gram of metallic lithium bit bybit, whereupon the reaction mixture turned to deep blue in color. Theblue color disappeared upon adding 5 ml. of ethanol to the mixture afterthe reaction had ended. The solvent was distilled off and the residuewas dissolved in ice-water. The solution was extracted with ether. Theether layer was separated from the aqueous layer. The ethereal extractwas dehydrated and mixed with an ethereal solution of oxalic acid toseparate 0.5 grams of crystals, which were recrystallized from ethanolto give 4- dimethylamino-l ,Z-dithiolane hydrogen oxalate melting atl69l 70 with decomposition.

The aqueous layer separated from the ethereal extract was alkalified.Benzoyl chloride was added to the alkaline aqueous solution to allow thereaction to take place. The reaction mixture was extracted with etherand the ethereal extract was processed in an ordinary manner to give 0.4gram of 1,2- bis(benzoylthio)-3-dimethylaminopropane hydrogen oxalatewhich melts 156 decomposition.

Instead of the metallic lithium above-used in this example, 1 gram ofmetallic sodium was used to carry out the reaction with the essentiallysame result as mentioned above.

EXAMPLE 35.

One gram of 4-dimethylaminomethyl-2-phenyl-1,3- dithiolane was dissolvedin a mixture of ml. of ether and 50 ml. of liquid ammonia. To thesolution under agitation, 0.5 gram of metallic lithium was added,whereupon the reaction mixture turned to deep blue in color. After 6 ml.of methanol was gradually added to the reaction mixture, the solvent wasdistilled off under reduced pressure. The residue was dissolved in waterand the solution was extracted with ether. An ethereal solution ofoxalic acid was added to the ethereal extract separated from the aqueouslayer to give 0.4 gram of 4- dimethylamino-1,2-dithiolane hydrogenoxalate, melting at 169 with decomposition.

Benzoyl chloride was added to the alkaline aqueous layer separated fromthe ethereal extract and the reaction mixture was treated in the sameway as in the preceding example to obtain 0.3 gram of 1 ,2-bis(benzoylthio)-3- dimethylaminopropane hydrogen oxalate, melting at 156with decomposition.

EXAMPLE 36.

To a solution of 2.7 grams of 2-phenyl-5-dimethyIamino-l ,3 -dithianehydrogen oxalate dissolved in 100 ml. of water was added an aqueoussolution of mercuric chloride. The mixture was warmed on water bath for10 minutes, whereupon benzaldehyde was produced and a mercaptideprecipitated. The precipitate was filtered to obtain 4 grams of crudemercaptide melting at 100-l09 with decomposition. The crude mercaptidewas suspended in 100 ml. of water and hydrogen sulfide was introducedinto the suspension. After filtration, the filtrate was adjusted to pH8.0 and extracted with ether. The ethereal extract was dehydrated andmixed with an ethereal solution of oxalic acid to obtain 1.8 grams of1,3-dimercapto- Z-dimethylaminopropane hydrogen oxalate melting at 150with decomposition.

EXAMPLE 37.

1,3-DichIoro-2-dimethylaminopropane hydrochloride in an amount of 9.6grams was allowed to react with 24.8 grams of sodium thiosulfate inwater to give an aqueous solution of the disodium salt ofI,3-bis(sulfothio)-2-dimethylaminopropane. The aqueous solution wasdropped into an aqueous solution of 7.5 grams of disodium salt of1,3-dimercapto-2- dimethylaminopropane, which had been saturated withsodium chloride and thoroughly cooled with ice-water. The resultingreaction mixture was extracted with ether. The ethereal extract waswashed with water and dried. An anhydrous ethereal solution of oxalicacid was added to the dried ethereal solution to separate crystals,which were filtered and recrystallized from a mixture of ethanol andether to give 4.2 grams of 4,6-bis(dimethylamino l ,2,6,7-tetrathiecanedihydrogen dioxalate as pale yellow leaflets melting at l54156 withdecomposition.

EXAMPLE 3 8.

Into a solution of 1,3-dimercapto-7-dimethylaminoheptane in methanol,prepared by adding 2.5 grams of sodium boron hydride into a solution of5.1 grams of 3-dimethylaminobutyl- 1,2-dithiolane in 50 ml. of methanoland by allowing the mixture to stand for 20 minutes-, there was added 17grams of benzyl chloride, and the mixture was stirred for 5 minutes atroom temperature and for further 1 hour on water bath. The reactionmixture was concentrated to leave an oily substance, which was extractedwith ether. The ethereal solution was washed with water and dried overanhydrous sodium sulfate. An ethereal solution of anhydrous oxalic acidwas added to the dried ethereal solution to separate yellow oil. Theyellow oil was collected, mixed with 20 percent aqueous potassiumsolution and extracted with ether. The ethereal solution was washed withwater, dried and concentrated to give 1.3 grams of 1,3-bis(benzylthio)-7-dimethylaminoheptane as an undistil- Iable oil.

COMPOSITION 1.

One part of l,3-bis(benzylthio)-2-diethylaminopropane was adsorbed on1.5 parts of diatomaceous earth and admixed with 1.5 parts of silicicacid (white carbon). The mixture was diluted with 96 parts of tale toprepare 1 percent dust composition to be used for fruit trees.

COMPOSITION 2.

In 30 parts of methyl ethyl ketone was dissolved 5 parts ofl,3-dithiocyanate-Z-dimethylaminopropane, and to the solution was addeda solution of 10 parts of a surfactant (which mainly consists of 70percent of polyoxyethylenealkylphenylethers and 30 percent of sodiumarylsulfonates and is sold by Takemoto-Yushi Co., Japan under the tradename Newkalgen 1515') in 55 parts of toluene to prepare 5 percentemulsifiable solution to be used for rice plants.

COMPOSITION 3.

Forty-five parts of finely pulverized 1,3-dimercapto-2-dimethylaminopropane hydrogen oxalate was mixed with 5 parts of silicicacid (the aqueous suspension of which is neutral), and to the mixturewere added 48 parts of the finegrained clay used in papermaking and 2parts of sodium ligninsulfonate. The mixture was finely pulverized andadmixed to prepare 45 percent wettable powder to be used for vegetables.

COMPOSITION 4.

A solution of 5 parts of abietic acid polyglycol ester in 10 parts ofacetone was adsorbed on 35 parts of finely pulverized1,2-dimercapto-3-dimethylaminopropane hydrogen oxalate and the mixturewas dried in air at a temperature lower than 60. To the dried mixturewere added 58 parts of finely grained clay and 2 parts of sodiumligninsulfonate and the Inna.

mixture was thoroughly pulverized and admixed to prepare 35 percentwettable powder to be used for fruit trees.

COMPOSITION 5.

COMPOSITION 6.

In a mixture of parts of cyclohexanone and 30 parts of methylnaphthalenewas dissolved parts of 4- dimethylaminomethyl-l,3-dithiolane2-thione. Tothe solution was added parts of a surfactant (which mainly consists of70 percent of polyoxyethylenealkylphenylethers and 30 percent of organicsulfonates and is sold by Takemoto-Yushi Co., Japan under the trade nameNewkalgen ISS-H") and the mixture was uniformly dissolved underagitation to prepare 25 percent emulsifiable solution to be used tives.

for vegeta- COMPOSITION 7.

In 50 parts of ethylene glycol monomethyl ether was dissolved 15 partsof l,3-bis(dimethoxyphosphinothioylthio)-2- dimethylaminopropanehydrogen oxalate. Into the solution were added and dissolved 20 parts ofa surfactant (which mainly consists of 70 percent of polyoxyethylenealkylphenylethers and 30 percent of organic sulfonates and is sold byToho Kagaku Co., Japan under the trade name Sorpol 2283T") and 15 partsof xylene, to prepare 15 percent emulsifiable solution to be used forfruit trees.

COMPOSITION 8.

One and half parts of 1,3-bis( amidinothio)-2- dimethylaminopropanehydrogen oxalate dihydrochloride, 0.5 part of silicic acid and 8 partsof talc were admixed and finely pulverized. The pulverized mixture wasdiluted with 90 parts of the clay, whose apparent specific gravity wasabout 0.5-0.6, to prepare 1.5 percent dust composition to be used forfruit trees.

COMPOSITION 9.

Fifty parts of l ,2-bis( ethoxythiocarbonylthio )-3-dimethylaminopropane was mixed with 15 parts of benzene, 15 parts of asurfactant (which mainly consists of polyoxyethylenediphenylethers andis sold by Takemoto-Yushi Co., Japan under the trade name Newkalgen2005) and 20 parts of another surfactant (which mainly consists ofpolyoxyethylenealkylphenylethers and is sold by Takemoto-Yushi Co.,Japan under the trade name Newkalgen P-55) to prepare 50 percentemulsifiable solution to be used for fruit trees.

COMPOSITION 10.

In 8 parts of methanol was dissolved 2 parts of 4,9-bis(dimethylamino)-l,2,6,7-tetrathiecane under warming. The solution wassprayed on parts of talc, which had been warmed at a temperature ofabout to 60 in ribbon blender with heating jacket, whereupon theprincipal ingredient was adsorbed on the tale and methanol was drivenoff as its vapor.

' The talc adsorbing the principal ingredient was diluted with 63 partsof dicalite (a kinof clay) to prepare 2 percent dust composition to beused for vegetables.

COMPOSITION l l.

Fifty pans of l,2-bis(isopropyldithio )-3- dimethylaminopropane hydrogenoxalate was pulverized in a fluid energy mill and was mixed with 50parts of potassium chloride. The mixture was again pulverized in adisintegrator to prepare 50 percent wettable powder to be used forvegetables.

COMPOSITION 12.

Ten parts of l,3-bis(benzyldithio )-2- dimethylaminopropane hydrogenoxalate was pulverized. To

the pulverized compound were added 2 parts of sodium ligninsulfonate, 5parts of polyoxyethyleneoctylphenylether, 3 parts of silicic acid andparts of clay, and the mixture was thoroughly admixed to prepare 10percent wettable powder.

COMPOSITION 13.

Forty parts of l,3-bis(ethylthio )-2-piperidinopropane hydrogen oxalatewas pulverized. To the pulverized compound were added 2 parts of sodiumIigninsulfonate, 5 parts of polyoxyethyleneonylphenylether, 6 parts ofsilicic acid and 47 parts of fine-grained clay, and the mixture wasthoroughly admixed to prepare 40 percent wettable powder.

COMPOSITION 14.

Two parts of thoroughly pulverized 1,3-bis(ethoxythiocarbonylthio)-2-diethylaminopropane hydrogen oxalate wasdiluted with 98 parts of talc to prepare 2 percent dust composition.

We claim: I. A compound of the formula l assa e wherein R representsN,N-diloweralkylthiocarbamoyl and R and R independently represent loweralkyl, cyclohexyl and phenyl.

2. l,3-Bis(N,N-diethylthiocarbamoylthio)-2- dimethylaminopropane.

* l l i l "new.

2. 1,3-Bis(N,N-diethylthiocarbamoylthio)-2-dimethylaminopropane.